【作者】 朱贤锋；

【导师】 彭金华；

【作者基本信息】 南京理工大学 ， 安全技术及工程， 2008， 硕士

【摘要】 向沸腾状态下的甲苯滴加浓硫酸进行磺化反应具有一定的危险性。本文主要通过实验室全自动反应量热仪（RCle）测试了这一半间歇磺化过程的热力学数据,从而进行反应过程的安全性研究。首先采用差示扫描量热仪（DSC）对反应体系及产物在非等温状态下的热分解行为进行研究和分析,判断不同温度阶段发生的反应类型;再采用RCle研究不同的加料速度对反应过程参量的影响,并初探了苯环上甲基对磺化反应的影响,计算出间歇式反应失控条件下的绝热温升(△T_ad)、反应所能达到的最高温度（MTSR）等参数;用加速度量热仪（ARC）对反应产物在绝热状态下的热分解行为进行了研究,得出不回归温度T_NR和至热爆炸发生的剩余时间仅为24h所对应的温度ADT₂₄等参数:最后结合ARC数据和RCle数据,根据热失控危险等级分类标准进行热失控危险等级划分。结果表明:采用半间歇式反应模式可以使反应失控严重度大大降低,然而该半间歇式反应在设定操作条件下反应失控所导致的最大温升（MTSR）还是超出安全条件允许的范围,而且该反应的热失控危险等级为第四级,比较危险,虽然足够多的甲苯能起到一定的安全保护作用,但还应从工艺上加以优化,以保证生产安全。更多还原

【Abstract】 The sulphonation by dosing concentrated sulfuric acid to boiling toluene is of some risks. In this paper, Reaction Calorimeter（RC1e） was used to measure the thermodynamics parameters of this sulphonation in semi-batch reactor. First of all, the thermal decomposition behaviors of products and reaction system under non-isothermal mode were studied by Differential Scanning Calorimeter（DSC）. Then a series of experiments were carried out with RC1e to study the influence of dosing time, and a primary try on the influence of methyl to sulphonation was performed as well; Some parameters such as adiabatic temperature increasement of batch reaction(ΔT_ad), maximum temperature of synthetic reaction（MTSR） were obtained here. After that, Accelerating Rate Calorimeter （ARC） were used to study the thermal decomposition of the product; the important parameters temperature of no return(T_NR) and the temperature when the explosion happened on 24h(ADT₂₄) are analyzed. Finally, combining the datum from ARC and RC1e, the risk class of thermal runaway criticality was studied. The results indicate that the severity of thermal runaway of the sulphonation of toluene with concentrated sulfuric acid can be reduced greatly by using semi-batch reaction, the MTSR under given operating conditions is still out of the scale. And its risk class of thermal runaway reaction is class 4, that means, though there is enough toluene in reaction system, which can restrain temperature rise at it’s boiling point, it is still necessary to optimize the technics to confirm safety production.更多还原